金属有机化学教案8.pdf

第十三章烯丙基和二烯基络合物 Allyl ligands are ambidentate ligands that can bind in both a monohapto and trihapto form. The trihapto form can be expressed as a number of difference resonance forms as shown here for an unsubstituted allyl ligand: Counting electrons : For the monohapto form, simply consider it to be an alkyl ligand (1 or 2 electron donor depending which formalism you use). In the trihapto form, it is easiest to think of it as an alkyl (1 or 2 electrons) + a neutral alkene (2 electrons) for a total of 3 or 4 electrons donated. 中国科学技术大学 Structure and Bonding In the trihapto form, the C-C distances and bond angles are about what wed expect, 1.35 to 1.40 Å with a C-C-C angle of 120°. The two C-C bonds are usually the same length, but there are some exceptions, particularly when strongly pi- bonding ligands are trans to the allyl ligand. The plane of the allyl ligand is typically tilted away from perpendicular to maximize orbital overlap. Krüger et. al. report on the neutron diffraction structure of an allyl complex. They found that H and H are bent towards the metal (7 and meso syn 13°from planar) while H is bent 31° anti away. In this particular example, the Ni- C1 and Ni-C3 distances are approximately 2.03 Å and Ni-C2 is 1.98 Å: 中国科学技术大学 烯丙基镍16e，十分空气敏感。它具有Sandwich结构，配 体与金属键高度共价。 甲基烯丙基氯化鈀二聚体钯也是16e，烯丙基的两个末端 碳与钯距离较近，而中间那个碳离钯较远。 第一过渡周期金属的烯丙基化合物的热稳定性低于第二、 三过渡周期金属的烯丙基化合物。例如Co(allyl)3在−55°C 以上分解，而Rh(allyl)3在室温以上还稳定。 中国科学技术大学 Synthesis of Allyl Complexes Most syntheses of trihapto allyl complexes involve the synthesis of a monohapto complex which then displaces a ligand to give the trihapto form. Common methods for the synthesis